Polymeric films for second order nonlinear optics

Abstract

Films of a multiplicity of adjacent polymeric, amphiphilic monolayers, said film having second order optical nonlinearity which increases with the number of active monolayers are provided, as well as novel polymers from which said films are prepared.

What is claimed is: 
     
       1. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein at least every third monolayer comprises a polymer having substituent groups each containing a second order nonlinearly polarizable chromophore, and each terminated by a hydrophobic moiety comprising a branched or linear fluorocarbon group;   wherein the remaining monolayers each comprise a polymer having substituent groups with weak or no nonlinear polarizability, and   wherein one or more of the polymers have a hydrophilic backbone.   
     
     
       2. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein at least every third monolayer comprises a polymer having substituent groups containing a second order nonlinearly polarizable chromophore;   wherein the remaining monolayers each comprise a polymer having substituent groups with weak or no nonlinear polarizability terminated by a hydrophobic moiety comprising a branched or linear fluorocarbon group; and   wherein one or more of the polymers have a hydrophilic backbone.   
     
     
       3. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein at least every second monolayers comprises a polymer A having substituent groups each containing a second order nonlinearly polarizable chromophore and each terminated by a hydrophobic moiety comprising a branched or linear fluorocarbon group;   wherein the remaining monolayers each comprise a polymer having substituent groups 1) with weak or no nonlinear polarizability, or 2) containing a chromophore having second order nonlinear polarizability opposite in sign relative to said chromophore of polymer A; and   wherein one or both of the polymers have a hydrophilic backbone.   
     
     
       4. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein at least every second monolayer comprises a polymer having substituent groups containing a second order nonlinearly polarizable chromophore, and   wherein the remaining monolayers each comprise a polymer having substituent groups with weak or no nonlinear polarizability terminated by a hydrophobic moiety comprising a branched or linear fluorocarbon group, and   wherein one or both of the polymers have a hydrophilic backbone.   
     
     
       5. The film of claims 1, 2, 3, or 4 wherein the hydrophilic backbone comprises a) a N-substituted polyethyleneimine homopolymer of three or more repeating units, b) a polyacrylate homopolymer of three or more repeating units, c) a polymethacrylate homopolymer of three or more repeating units, or d) a copolymer of polyacrylate, polymethacrylate, or N-substituted polyethyleneimine. 
     
     
       6. The film of claims 1, 2, 3, or 4 wherein the fluorocarbon group comprises a C 6  to C 12  perfluoroalkyleneoxy group. 
     
     
       7. The film of claims 1, 2, 3, or 4 wherein the fluorocarbon group comprises CF 3  (CF 2 ) n  -- wherein n is greater than or equal to 4. 
     
     
       8. The film of claim 1, 2, 3, or 4 wherein the fluorocarbon group comprises branched [CF 3 ) 2  CF] 2  C═C(CF 3 )O--. 
     
     
       9. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein the polymeric monolayers comprise repeating groups of two monolayers, each said repeating group comprising one layer A of a polymer having repeating units of formula (1), (2), or (3) combined with one layer B of a polymer having repeating units of formula (4), (5) or (7), wherein formulae (1) through (5) and (7) have the following structures ##STR14## wherein R f  for formulae (1), (2), (4) and (5) is a linear, branched or cyclic perfluoroalkyl group having at least 4 carbon atoms and having 0 to 3 double bonds; R f  for formula (3) is (CX 2 ) t  X; X is F or H, and t is an integer of from 1 to 18;   A for formulae (1) and (2) is phenylene or stilbeneyl;   A for formula (3) is phenylene;   Y is O, S or NR 1  ; provided that when Y is NR 1 , A for formula (2) is phenylene, stilbeneyl or biphenylene;   R is C 6  to C 20  alkyl;   R 1  is H or C 1  to C 5  alkyl;   R 2  and R 3  are each independently H or C 1  to C 5  alkyl;   R 4  and R 5  are each independently H or C 1  to C 17  alkyl;   m is an integer from 2 to 5;   n is an integer of at least 3;   p is an integer from 0 to 5, provided that p is 1 when Y is NR 1  and A is biphenylene;   q is an integer from 2 to 3;   r is an integer of at least 3;   s is an integer from 0 to 17;   x is an integer from 2 to 3; and   a and b are each independently an integer of at least 2.   
     
     
       10. A film comprising at least ten adjacent monolayers of amphiphilic polymers, said film having second order optical nonlinearity which increases with the number of said monolayers which are nonlinear optically active, wherein said monolayers repeat in groups of three as ABB or AB 1  B 2  in which each repeating unit exhibits a net polar alignment and comprises a) one monolayer A of an amphiphilic polymer, and   b) two monolayers B of a distinct amphiphilic polymer having opposite orientation to each other, or two monolayers B 1  and B 2  which are distinct from each other as well as distinct from monolayer A and have opposite orientation to each other, wherein monolayer A comprises a polymer having repeating units of formula (6) and each monolayer B, B 1  or B 2  comprises a polymer having repeating units of formula (4), (5) or (7) wherein formulae (4), (5), (6), and (7) have the following structures ##STR15##  wherein R f  is a linear, branched or cyclic perfluoroalkyl group having at least 4 carbon atoms and having 0 to 3 double bonds;   Z is OR 6  or Cl;   R is C 6  to C 20  alkyl;   n is an integer of at least 3;   a is an integer of at least 2;   b is an integer of at least 2; and   x is an integer from 2 to 3; provided that for formula (6) the ratio of a/b is 0.1 to 1.